title: Silicon acceleration of a tandem alkene isomerization/electrocyclic ring-opening of 2-methyleneoxetanes to α,β-unsaturated methylketones.
abstract: The first rearrangement of 2-methyleneoxetanes to α,β-unsaturated methylketones is reported. It is proposed that when these substrates are heated, the corresponding oxetenes are formed and subsequently undergo electrocyclic ring-opening to methyl vinylketones. In particular, α-silyl-α,β-unsaturated methylketones were isolated in moderate to high yields and with high stereoselectivities. Based on the proposed mechanism, density functional theory explains the differential kinetics and stereoselectivities among substrates.
authors.affiliation: Department of Chemistry, University of Connecticut , Storrs, Connecticut 06269-3060, United States.
authors.forename: Elisa
authors.initials: E
authors.lastname: Farber
authors.forename: Aleksandra
authors.initials: A
authors.lastname: Rudnitskaya
authors.forename: Santosh
authors.initials: S
authors.lastname: Keshipeddy
authors.forename: Kendricks S
authors.initials: KS
authors.lastname: Lao
authors.forename: José A
authors.initials: JA
authors.lastname: Gascón
authors.forename: Amy R
authors.initials: AR
authors.lastname: Howell